CN110872378A - Random conjugated copolymer, preparation method thereof and application thereof in organic photoelectric element - Google Patents
Random conjugated copolymer, preparation method thereof and application thereof in organic photoelectric element Download PDFInfo
- Publication number
- CN110872378A CN110872378A CN201811142925.4A CN201811142925A CN110872378A CN 110872378 A CN110872378 A CN 110872378A CN 201811142925 A CN201811142925 A CN 201811142925A CN 110872378 A CN110872378 A CN 110872378A
- Authority
- CN
- China
- Prior art keywords
- group
- independently
- carbons
- conjugated copolymer
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims description 60
- 238000013086 organic photovoltaic Methods 0.000 claims description 40
- 125000001246 bromo group Chemical group Br* 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 33
- 125000003342 alkenyl group Chemical group 0.000 claims description 24
- 125000000304 alkynyl group Chemical group 0.000 claims description 24
- 239000004065 semiconductor Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 230000005525 hole transport Effects 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical group 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005893 bromination reaction Methods 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 230000031709 bromination Effects 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229920000547 conjugated polymer Polymers 0.000 description 9
- -1 heteroaryl radical Chemical class 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- DLQYXUGCCKQSRJ-UHFFFAOYSA-N tris(furan-2-yl)phosphane Chemical compound C1=COC(P(C=2OC=CC=2)C=2OC=CC=2)=C1 DLQYXUGCCKQSRJ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 229920002873 Polyethylenimine Polymers 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 238000000944 Soxhlet extraction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- AOOYMUMUMFGBDO-UHFFFAOYSA-N tributyl-(4-dodecylthiophen-2-yl)stannane Chemical compound CCCCCCCCCCCCC1=CSC([Sn](CCCC)(CCCC)CCCC)=C1 AOOYMUMUMFGBDO-UHFFFAOYSA-N 0.000 description 4
- OEKNWJQSAYEBFD-UHFFFAOYSA-N 2-(2-hexyldecyl)thiophene Chemical compound CCCCCCCCC(CCCCCC)CC1=CC=CS1 OEKNWJQSAYEBFD-UHFFFAOYSA-N 0.000 description 3
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 description 3
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 2
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 2
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 2
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 2
- KQZLRWGGWXJPOS-NLFPWZOASA-N 1-[(1R)-1-(2,4-dichlorophenyl)ethyl]-6-[(4S,5R)-4-[(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]-5-methylcyclohexen-1-yl]pyrazolo[3,4-b]pyrazine-3-carbonitrile Chemical compound ClC1=C(C=CC(=C1)Cl)[C@@H](C)N1N=C(C=2C1=NC(=CN=2)C1=CC[C@@H]([C@@H](C1)C)N1[C@@H](CCC1)CO)C#N KQZLRWGGWXJPOS-NLFPWZOASA-N 0.000 description 2
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 2
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 2
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 2
- ISRPCLCPFYVEHU-UHFFFAOYSA-N 7-(iodomethyl)pentadecane Chemical compound CCCCCCCCC(CI)CCCCCC ISRPCLCPFYVEHU-UHFFFAOYSA-N 0.000 description 2
- 229940126657 Compound 17 Drugs 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229940125797 compound 12 Drugs 0.000 description 2
- 229940126543 compound 14 Drugs 0.000 description 2
- 229940125758 compound 15 Drugs 0.000 description 2
- 229940126142 compound 16 Drugs 0.000 description 2
- 229940126086 compound 21 Drugs 0.000 description 2
- 229940127204 compound 29 Drugs 0.000 description 2
- 229940125877 compound 31 Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- URMVZUQDPPDABD-UHFFFAOYSA-N thieno[2,3-f][1]benzothiole Chemical compound C1=C2SC=CC2=CC2=C1C=CS2 URMVZUQDPPDABD-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 1
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- XULHFMYCBKQGEE-MRXNPFEDSA-N 2-Hexyl-1-decanol Natural products CCCCCCCC[C@H](CO)CCCCCC XULHFMYCBKQGEE-MRXNPFEDSA-N 0.000 description 1
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 1
- TVTJUIAKQFIXCE-HUKYDQBMSA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynyl-1H-purine-6,8-dione Chemical compound NC=1NC(C=2N(C(N(C=2N=1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C)=O TVTJUIAKQFIXCE-HUKYDQBMSA-N 0.000 description 1
- XULHFMYCBKQGEE-UHFFFAOYSA-N 2-hexyl-1-Decanol Chemical compound CCCCCCCCC(CO)CCCCCC XULHFMYCBKQGEE-UHFFFAOYSA-N 0.000 description 1
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 1
- RFKWIEFTBMACPZ-UHFFFAOYSA-N 3-dodecylthiophene Chemical compound CCCCCCCCCCCCC=1C=CSC=1 RFKWIEFTBMACPZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BQXUPNKLZNSUMC-YUQWMIPFSA-N CCN(CCCCCOCC(=O)N[C@H](C(=O)N1C[C@H](O)C[C@H]1C(=O)N[C@@H](C)c1ccc(cc1)-c1scnc1C)C(C)(C)C)CCOc1ccc(cc1)C(=O)c1c(sc2cc(O)ccc12)-c1ccc(O)cc1 Chemical compound CCN(CCCCCOCC(=O)N[C@H](C(=O)N1C[C@H](O)C[C@H]1C(=O)N[C@@H](C)c1ccc(cc1)-c1scnc1C)C(C)(C)C)CCOc1ccc(cc1)C(=O)c1c(sc2cc(O)ccc12)-c1ccc(O)cc1 BQXUPNKLZNSUMC-YUQWMIPFSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- XRWSZZJLZRKHHD-WVWIJVSJSA-N asunaprevir Chemical compound O=C([C@@H]1C[C@H](CN1C(=O)[C@@H](NC(=O)OC(C)(C)C)C(C)(C)C)OC1=NC=C(C2=CC=C(Cl)C=C21)OC)N[C@]1(C(=O)NS(=O)(=O)C2CC2)C[C@H]1C=C XRWSZZJLZRKHHD-WVWIJVSJSA-N 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125810 compound 20 Drugs 0.000 description 1
- 229940126208 compound 22 Drugs 0.000 description 1
- 229940125833 compound 23 Drugs 0.000 description 1
- 229940125961 compound 24 Drugs 0.000 description 1
- 229940125846 compound 25 Drugs 0.000 description 1
- 229940125851 compound 27 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/122—Copolymers statistical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/92—TFT applications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/95—Use in organic luminescent diodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The present invention provides a random conjugated copolymer comprising at least three different repeating units arranged in a random manner. Furthermore, one of the repeating units in the main chain of the random conjugated copolymer is connected with different conjugated linking units on both sides of the electron acceptor unit, so that the random conjugated copolymer has excellent photoelectric conversion characteristics. In addition, the invention also provides a preparation method of the random conjugated copolymer and an organic photoelectric element, wherein the preparation steps can be saved.
Description
Technical Field
The invention relates to an organic random conjugated copolymer (organic random copolymer), a preparation method thereof and application thereof in organic photoelectric elements, and organic photoelectric elements and devices comprising organic light-emitting diodes (organic light-emitting diodes), organic thin film transistors (organic thin film transistors), organic photovoltaic elements (organic photovoltaics) and organic photodetectors (organic photodetectors) containing the random conjugated copolymer.
Background
There are increasing applications of conjugated polymers in electronic devices such as organic light-emitting diodes (organic light-emitting diodes), organic thin film transistors (organic thin film transistors), organic photovoltaic devices (OPVs), and Organic Photodetectors (OPDs). Because the conjugated polymer material can be used for manufacturing electronic elements by using dip coating, spin coating, slit coating, screen printing, ink jet printing and other methods, compared with the method of coating by using an inorganic material to manufacture electronic elements by using a vacuum process, the method of using the conjugated polymer material is easier to realize low-cost and large-scale production. The organic photovoltaic module of the new generation is manufactured by using a conjugated polymer as a material of a photovoltaic main absorption layer. Organic photovoltaics have several advantages: (1) the raw material source is easy to obtain, the cost is low, and the processing and the amplification are easy; (2) the functional characteristics are easy to adjust and optimize through the structural design; (3) the module process has mild conditions, is suitable for wet coating process, is easy for large-area production and effectively reduces the production cost.
Despite the advantages of organic photovoltaics, several problems remain to be overcome in commercialization. For example, in addition to the conversion efficiency of organic photovoltaics, the light absorption wavelengths, absorption intensities, energy level matching properties of the P-type material and the N-type material of the light absorption layer, and the like, there is also a large correlation between the crystal morphology after the P-type material and the N-type material are mixed and formed into a film and the conversion efficiency. In general, if the crystallinity of the conjugated polymer is good, the solubility thereof is low, which results in that an environmentally-unfriendly chlorine-containing solvent must be used for dissolution of the conjugated polymer and the subsequent coating processing feasibility is improved. Therefore, the development of a structure of a conjugated polymer that can be dissolved using a relatively environmentally friendly chlorine-free solvent (e.g., toluene, xylene) is one of important issues for industrialization.
In addition, chinese patent No. 102439059B discloses a conjugated polymer applied to an organic photovoltaic device. The conjugated polymer is represented by a random copolymer (or called random conjugated copolymer) of the following formula P:
*-[D-Ar1-A-Ar1]m-[D-Ar2-A-Ar2]n- (O-X-O) -formula P.
-[D-Ar1-A-Ar1]-repeat unit structure 1.
-[D-Ar2-A-Ar2]-repeat unit structure 2.
Wherein D is an electron supply unit, Ar1And Ar2Is a conjugated linking unit, a is an electron acceptor unit, the repeating unit structure 1 and the repeating unit structure 2 as a repeating unit (repeat unit) to form a random copolymer of the formula P. In this patent, a random copolymer of the formula P is one in which the same conjugated linking units Ar are linked to both sides of the electron acceptor unit A in the repeating unit structure 11And the same conjugated linking units Ar are respectively linked on both sides of the electron acceptor unit A in the repeating unit structure 22. Such copolymers can be modified by introducing a plurality of monomers for copolymerization, but also increase the production cost because a large number of different monomers need to be prepared.
The chinese patent 107586379a introduces an asymmetric structure during monomer synthesis to try to achieve the purpose of modifying the structure, however, it also requires more steps and results in the increase of the manufacturing cost.
Disclosure of Invention
Accordingly, the present invention provides a random conjugated copolymer in which different conjugated linking units are respectively linked to both sides of an electron acceptor unit in the main chain of the random conjugated copolymer, so that the random conjugated copolymer can be dissolved using a relatively environmentally friendly chlorine-free solvent (e.g., toluene, xylene) and has excellent photoelectric conversion characteristics. In addition, the invention also provides a preparation method of the random conjugated copolymer and an organic photoelectric element, wherein the preparation steps can be saved.
The present invention provides the random conjugated copolymer of the following formula I, which is composed of at least three repeating units in a random arrangement mode, wherein the three repeating units are different from each other, and the three repeating units are respectively of a first repeating unit structure, a second repeating unit structure and a third repeating unit structure:
wherein- [ D-Ar in formula I1-A-Ar1]-is a first repeating unit structure.
Wherein- [ D-Ar in formula I2-A-Ar2]-is a second repeating unit structure.
Wherein- [ D-Ar in formula I1-A-Ar2]-is a third repeating unit structure.
Wherein D in formula I is an electron supply unit, Ar1And Ar2Is a conjugated linking unit, A is an electron acceptor unit, and the first repeating unit structure, the second repeating unit structure and the third repeating unit structure are taken as repeating units to form the random conjugated copolymer of the formula I. The random conjugated copolymer of formula I is connected with the same conjugated connecting unit Ar at two sides of the electron acceptor unit A in the first repeating unit structure1And the same conjugated connecting units Ar are respectively connected to both sides of the electron acceptor unit A in the second repeating unit structure2And different conjugated connecting units Ar are respectively connected to both sides of the electron acceptor unit A in the third repeating unit structure1And a conjugated linking unit Ar2(ii) a And, at each occurrence, Ar1And Ar2Different.
Wherein a, b and c represent real numbers in mole fraction, a is not less than 0.005 and not more than 0.99, b is not less than 0.005 and not more than 0.99, c is not less than 0.005 and not more than 0.99, and the sum of a, b and c is 1.
The invention also provides a preparation method of the random conjugated copolymer, which is to mix Br-A-Br and Ar1-SnBu3And Ar2-SnBu3Coupled with total mixing of catalystAnd (3) carrying out a synthesis reaction, and then carrying out a bromination reaction on the obtained mixture to obtain an electron acceptor monomer combination of the following three electron acceptor monomers: Br-Ar1-A-Ar2-Br、Br-Ar1-A-Ar1Br and Br-Ar2-A-Ar2-Br. According to different dosages of Br-A-Br and Ar1-SnBu3And Ar2-SnBu3Designed to obtain the required Br-Ar1-A-Ar2-Br、Br-Ar1-A-Ar1Br and Br-Ar2-A-Ar2-Br three electron acceptor monomers in proportion to each other. Combining the electron acceptor monomer with the electron donor monomer Me3Sn-D-SnMe3Polymerization is carried out to obtain the random conjugated copolymer.
The invention also provides another preparation method of the random conjugated copolymer, which comprises the steps of firstly preparing Br-A-Br and Ar1-SnBu3Mixing with catalyst to make coupling reaction, adding Ar when the reaction is reached to desired condition2-SnBu3Continuing the reaction, the resulting mixture is then subjected to a bromination reaction to yield the following electron acceptor monomer combination of three electron acceptor monomers: Br-Ar1-A-Ar2-Br、Br-Ar1-A-Ar1Br and Br-Ar2-A-Ar2-Br. According to different dosages of Br-A-Br and Ar1-SnBu3And Ar2-SnBu3And the design of the feeding sequence can obtain the required Br-Ar1-A-Ar2-Br、Br-Ar1-A-Ar1Br and Br-Ar2-A-Ar2-Br three electron acceptor monomers in proportion to each other. Combining the electron acceptor monomer with the electron donor monomer Me3Sn-D-SnMe3Polymerization is carried out to obtain the random conjugated copolymer.
The random conjugated copolymer prepared by the preparation method can save preparation steps, so that the method has cost advantage in material amplification production. Meanwhile, the structure of the random conjugated copolymer formula I also improves the solubility, so the method is suitable for environment-friendly solvents and has the best advantage in the coating production process.
The invention also provides an organic photoelectric element which is an organic light-emitting diode, an organic thin film transistor, an organic photovoltaic element and an organic photodetector containing the random conjugated copolymer.
Drawings
Fig. 1 is a schematic structural diagram of an organic photovoltaic device according to an embodiment of the present invention.
Fig. 2 is a schematic structural view of an organic photovoltaic device according to another embodiment of the present invention.
Fig. 3 is a current density-voltage diagram of the organic photovoltaic elements of the example and comparative examples of the present invention.
Fig. 4 is a schematic structural view of an organic photovoltaic device according to still another embodiment of the present invention.
Wherein the reference numerals are explained as follows:
70 a substrate;
80 positive electrode;
90 an organic semiconductor layer;
91 an electron transport layer;
92 an active layer;
93 a hole transport layer;
100 negative electrode.
Detailed Description
The present invention is described in detail below with reference to preferred embodiments so that those skilled in the art can easily understand the benefits and effects disclosed in the specification of the present invention. However, the embodiments are examples, and the present invention is not limited thereto.
The present invention provides such random conjugated copolymers of the following formula I:
wherein a, b and c represent real numbers in mole fraction, a is not less than 0.005 and not more than 0.99, b is not less than 0.005 and not more than 0.99, c is not less than 0.005 and not more than 0.99, and the sum of a, b and c is 1.
In the random conjugated copolymer of formula I, a is at least one group selected from the group consisting of:
wherein the content of the first and second substances,
z is O, S, Se, NR2Or
n0Is 0, 1 or 2;
R1is H, F, Cl, -CN group, R16、-OR17radical-SR18Radical, -C (═ O) OR19A radical, aryl (aryl radical) or heteroaryl (heteroaryl radical); and the number of the first and second groups,
R2to R19Each independently is a linear, branched or cyclic alkyl group having from 4 to 30 carbons, or each independently is an alkenyl or alkynyl group having from 4 to 30 carbons in the chain, or each independently is an alkyl, alkenyl or alkynyl group having from 4 to 30 carbons in the chain in which one or more H groups are substituted with a halogen, -CN group or-Si group.
In the random conjugated copolymer of formula I, Ar1And Ar2Each independently is:
wherein the content of the first and second substances,
n1and n2Is 1,2 or 3;
R20to R23Each independently is a linear, branched or cyclic alkyl group having from 4 to 30 carbons, or each independently is an alkenyl or alkynyl group having from 4 to 30 carbons in the chain, or each independently is an alkyl, alkenyl or alkynyl group having from 4 to 30 carbons in the chain in which one or more H's are substituted with a halogen, -CN group or-Si group; or R20To R23Each independently is H,F. Cl, -CN, -OR24radical-SR25Radical, -C (═ O) OR26A radical, aryl (aryl radical) or heteroaryl (heteroaryl radical); and the number of the first and second groups,
R24to R26Each independently is a linear, branched or cyclic alkyl group having from 4 to 30 carbons, or each independently is an alkenyl or alkynyl group having from 4 to 30 carbons in the chain, or each independently is an alkyl, alkenyl or alkynyl group having from 4 to 30 carbons in the chain in which one or more H groups are substituted with a halogen, -CN group or-Si group.
In the random conjugated copolymer of formula I, D is:
wherein the content of the first and second substances,
R27to R28Each independently is H, F, Cl, R29-CN group, -OR30radical-SR31Radical, -C (═ O) OR32Aryl, heteroaryl or-Si (R)33)3A group;
R29to R33Each independently is a linear, branched or cyclic alkyl group having from 4 to 30 carbons, or each independently is an alkenyl or alkynyl group having from 4 to 30 carbons in the chain, or each independently is an alkyl, alkenyl or alkynyl group having from 4 to 30 carbons in the chain in which one or more H's are substituted with a halogen, -CN group or-Si group;
aryl (aryl group) is
Heteroaryl (heteroaryl) is
n3And n4Is 1,2, 3, 4 or 5;
R34to R37Each independently is H, F, Cl, R38-CN group, -OR39radical-SR40Radical, -C (═ O) OR41Radical or-Si (R)42)3A group;
R38to R42Each independently is a linear, branched or cyclic alkyl group having from 4 to 30 carbons, or each independently is an alkenyl or alkynyl group having from 4 to 30 carbons in the chain, or each independently is an alkyl, alkenyl or alkynyl group having from 4 to 30 carbons in the chain in which one or more H's are substituted with a halogen, -CN group or-Si group;
R43to R48Each independently is H, F, Cl, R49-CN group, -OR50radical-SR51Radical, -C (═ O) OR52Radical or-Si (R)53)3A group; and the number of the first and second groups,
R49to R53Each independently is a linear, branched or cyclic alkyl group having from 4 to 30 carbons, or each independently is an alkenyl or alkynyl group having from 4 to 30 carbons in the chain, or each independently is an alkyl, alkenyl or alkynyl group having from 4 to 30 carbons in the chain in which one or more H groups are substituted with a halogen, -CN group or-Si group.
The random conjugated copolymer of the present invention can be used to prepare an electron acceptor monomer combination of three electron acceptor monomers according to the following reaction scheme 1.
Reaction scheme 1 reacting Br-A-Br and Ar1-SnBu3And Ar2-SnBu3Mixing with palladium catalyst, coupling reaction, and mixing the obtained mixture (containing Ar)1-A-Ar2、Ar1-A-Ar1And Ar2-A-Ar2) Bromination is carried out to give the following electron acceptor monomer combinations of three electron acceptor monomers: Br-Ar1-A-Ar2-Br、Br-Ar1-A-Ar1Br and Br-Ar2-A-Ar2-Br. According to different dosages of Br-A-Br and Ar1-SnBu3And Ar2-SnBu3Designed to obtain the required Br-Ar1-A-Ar2-Br、Br-Ar1-A-Ar1Br and Br-Ar2-A-Ar2-Br three electron acceptor monomers in proportion to each other. Wherein Me isIs methyl, Bu is butyl, Br is bromine and Sn is tin.
Alternatively, the random conjugated copolymer of the present invention may be prepared as an electron acceptor monomer combination of three electron acceptor monomers according to the following reaction scheme 2.
Combining the electron acceptor monomer of the three electron acceptor monomers obtained in reaction scheme 1 or reaction scheme 2 with the electron donating monomer Me3Sn-D-SnMe3Polymerization is carried out to obtain the random conjugated copolymer.
The properties and effects of the present invention are described in detail by examples below. The examples are merely illustrative of the nature of the present invention and the present invention is not limited to the examples.
The following examples illustrate the preparation of the foregoing electron acceptor monomer combinations.
Example 1, electron acceptor monomer combination M1 was prepared according to reaction scheme 1:
3-dodecylthiophene (Compound 1) (50g,198.0mmol) was mixed with 500mL of anhydrous tetrahydrofuran in a round bottom flask, 2.5M n-butyllithium (79.2mL,198.0mmol) was added slowly at 0 ℃ and stirring was continued for one hour at 0 ℃. Tributyltin chloride (64.5g,198.0mmol) was then slowly added to the reaction and stirring continued at 0 ℃ for 30 min. After returning to room temperature, ethyl acetate and deionized water were added and extracted three times, and the organic layer was dried over anhydrous magnesium sulfate, filtered, concentrated and dried by a rotary concentrator to give 2-tributylstannyl-4-dodecylthiophene (compound 2) as a yellow liquid (99.3g, yield: 93%).
4, 7-dibromo-5, 6-difluorobenzo [1,2,5 ]]Thiadiazole (compound 4) (5.0g,15.2mmol), 2-tributylstannyl-4-dodecylthiophene (compound 2) (6.6g,12.2mmol), 2-tributylstannyl-thiophene (compound 3) (6.8g,18.2mmol), tris (2-furyl) phosphine (463mg,1.5mmol) and Pd2(dba)3(348mg,0.4mmol) was added to a round bottom flask followed by 50mL of toluene and stirred under nitrogen for three hours. After cooling, the toluene was removed using a rotary concentrator and purified by silica gel column chromatography (petroleum ether/dichloromethane) to give mixture A1(6.08g) as a yellow solid after drying in vacuo. The composition and quantitative analysis of mixture a1 by high performance liquid chromatography (hplc) (high performance liquid chromatography) were as follows: 25.9 percent of compound 5, 51.1 percent of compound 6, 22.3 percent of compound 7 and the balance of impurities.
Mixture A1(3.0g,6.0mmol) was added to a 100mL round-bottom flask followed by 15mL tetrahydrofuran. NBS (N-bromosuccinimide, 2.18g,12.3mmol) was added stepwise under exclusion of light, followed by heating to 45 ℃ and stirring for one hour. After the reaction, the solvent was removed by a rotary concentrator, and the mixture was purified by silica gel column chromatography (petroleum ether/dichloromethane), and dried under vacuum to obtain an orange solid, i.e., electron acceptor monomer combination M1(2.7 g). The electron acceptor monomer combination M1 was analyzed by HPLC to give the following composition and quantitative results: 25.3 percent of compound 8, 51.4 percent of compound 9, 22.4 percent of compound 10 and the balance of impurities.
Example 2, electron acceptor monomer combination M2 was prepared according to reaction scheme 1:
4, 7-dibromo-5-chlorobenzo [1,2,5 ]]Thiadiazole (compound 11) (5.0g,15.2mmol), 2-tributylstannyl-4-dodecylthiophene (compound 2) (8.9g,15.2mmol), 2-tributylstannyl-thiophene (compound 3) (5.7g,15.2mmol), tris (2-furyl) phosphine (463mg,1.5mmol) and Pd2(dba)3(348mg,0.4mmol) was added to a round bottom flask followed by 50mL of toluene, stirring at 55 ℃ for three hours under nitrogen, cooling and removal of toluene using a rotary concentrator, purification by silica gel column chromatography (petroleum ether/dichloromethane) and drying under vacuum to give mixture A2 as an orange solid (6.7 g). The composition and quantitative analysis of mixture a2 by HPLC gave: 8.2 percent of compound 12, 52.2 percent of compound 13, 38.9 percent of compound 14 and the balance of impurities.
Mixture A2(2.0g,3.4mmol) was added to a 100mL round bottom flask, followed by 10mL tetrahydrofuran and NBS (1.3g,7.0mmol), followed by heating to 45 ℃ and stirring for one hour. After completion of the reaction, the solvent was removed using a rotary concentrator, and the mixture was purified by silica gel column chromatography (petroleum ether/dichloromethane), and dried under vacuum to obtain electron acceptor monomer combination M2(1.5g) as a red solid. The electron acceptor monomer combination M2 was analyzed by HPLC to give the following composition and quantitative results: 6.4 percent of compound 15, 46.8 percent of compound 16, 46.3 percent of compound 17 and the balance of impurities.
Example 3, electron acceptor monomer combination M3 was prepared according to reaction scheme 2:
4, 7-dibromo-5-chlorobenzo [1,2,5 ]]Thiadiazole (Compound 11) (5.0g,15.2mmol), 2-tributylstannyl thiophene (Compound 3) (5.7g,15.2mmol), tris (2-furyl) phosphine (463mg,1.5mmol) and Pd2(dba)3(348mg,0.4mmol) was added to a round bottom flask followed by 50mL of toluene and stirring at 55 deg.C for two hours under nitrogen, followed by addition of 2-tributylstannyl-4-dodecylthiophene (Compound 2) (8.9g,15.2mmol) to the reaction and stirring with continued heating for three hours. After cooling, the toluene was removed using a rotary concentrator and purified by silica gel column chromatography (petroleum ether/dichloromethane) to give mixture A3(5.8g) as an orange solid after drying in vacuo. The composition and quantitative analysis of mixture a3 by HPLC gave: 5.3 percent of compound 12, 74.6 percent of compound 13, 19.1 percent of compound 14 and the balance of impurities.
Mixture A3(2.0g,3.8mmol) was added to a 100mL round bottom flask, followed by 10mL tetrahydrofuran and NBS (1.4g,7.8mmol), followed by heating to 45 ℃ and stirring for one hour. After completion of the reaction, the solvent was removed using a rotary concentrator, and the mixture was purified by silica gel column chromatography (petroleum ether/dichloromethane), and dried under vacuum to obtain electron acceptor monomer combination M3(1.96g) as a red solid. The electron acceptor monomer combination M3 was analyzed by HPLC to give the following composition and quantitative results: 2.9 percent of compound 15, 79.7 percent of compound 16, 17.0 percent of compound 17 and the balance of impurities.
Example 4, electron acceptor monomer combination M4 was prepared according to reaction scheme 1:
compound 18(10.7g,29.3mmol) was mixed with 100mL of anhydrous tetrahydrofuran in a round bottom flask, 2.5M n-butyllithium (12.9mL,32.3mmol) was added slowly at 0 deg.C and stirring was continued for one hour at 0 deg.C. Tributyltin chloride (11.4g,35.2mmol) was then slowly added to the reaction and stirring continued at 0 ℃ for 30 min. After returning to room temperature, deionized water was added thereto and extracted three times, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated and drained by a rotary concentrator to obtain compound 19(18.2g, yield: 95%) as a yellow liquid.
Compound 20(3.0g,7.2mmol) was mixed with 30mL of anhydrous tetrahydrofuran in a round bottom flask, 2.5M n-butyllithium (3.1mL,7.8mmol) was added slowly at 0 deg.C and stirring was continued for one hour at 0 deg.C. Tributyltin chloride (2.8g,8.6mmol) was then slowly added to the reaction and stirring continued at 0 ℃ for 30 min. After returning to room temperature, ethyl acetate and deionized water were added and extracted three times, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated and pumped off by a rotary concentrator to obtain compound 21(4.9g, yield: 97%) as a yellow liquid.
4, 7-dibromo-5, 6-difluorobenzo [1,2,5 ]]Thiadiazole (compound 4) (1.3g,3.9mmol), compound 19(2.4g,3.6mmol), compound 21(3.1g,4002E3mmol), tris (2-furyl) phosphine (122mg,0.4mmol) and Pd2(dba)3(92mg,0.1mmol) was added to a round bottom flask followed by 15mL of toluene and heated to reflux overnight under nitrogen. After cooling, the toluene was removed using a rotary concentrator and purified by silica gel column chromatography (petroleum ether) to give mixture A4(1.3g) as an orange solid after vacuum drying. The composition and quantitative analysis of mixture a4 by HPLC gave: 31.9 percent of compound 22, 48.1 percent of compound 23, 19.1 percent of compound 24 and the balance of impurities.
Mixture A4(1.0g,1.0mmol) was added to a 100mL round bottom flask, followed by 10mL tetrahydrofuran and NBS (378mg,2.1mmol), followed by heating to 45 ℃ and stirring for one hour. After the reaction, the solvent was removed by a rotary concentrator, and the mixture was purified by silica gel column chromatography (petroleum ether) and dried under vacuum to obtain an electron acceptor monomer combination M4(1.1g) as a red solid. The electron acceptor monomer combination M4 was analyzed by HPLC to give the following composition and quantitative results: 32.0% of compound 25, 48.6% of compound 26, 18.6% of compound 27, and the balance impurities.
The following examples illustrate the preparation of the foregoing electron donating monomers.
Example 5, preparation of electron donating monomer D1: 4, 8-bis (5- (2-hexyldecyl) thiophen-yl) benzo [1,2-b:4, 5-b' ] dithiophene bistrimethyltin.
2-hexyl-1-decanol (Compound 28) (50g,0.20mol) was charged under nitrogen to a 1L reaction flask, 300mL of methylene chloride was added, iodine (68g,0.26mol) and imidazole (18.3g,0.26mol) were added, stirring was carried out at room temperature for 10 minutes, triphenylphosphine (70.3g,0.26mol) was added at 10 ℃ and stirring was carried out at room temperature for 15 hours. 100mL of saturated sodium thiosulfate was added and the mixture was extracted and washed 2 times, dried over anhydrous magnesium sulfate, and concentrated to remove the solvent, whereby 58.1g of 1-iodo-2-hexyldecane (Compound 29) was obtained as a pale yellow liquid in a yield of 80%.
Thiophene (29.9g,0.35mol) was charged into a 2L reaction flask under nitrogen, 500mL of anhydrous tetrahydrofuran was added, n-butyllithium (136.2mL,0.30mol) was added dropwise at 10 ℃, stirring at room temperature for 1 hour, 1-iodo-2-hexyldecane (compound 29) (50g,0.14mol) was added, stirring at room temperature for 15 hours, 50mL of water was slowly added at 10 ℃, 100mL of n-hexane was added and extracted 2 times, anhydrous magnesium sulfate was dried, the solvent was removed by concentration, and 30.5g of 2- (2-hexyldecyl) thiophene (compound 30) as a pale yellow liquid was obtained by purification by distillation, with a yield of 70%.
Charging 2- (2-hexyldecyl) thiophene (compound 30) (50g,0.16mol) into a 2L reaction flask under nitrogen, adding 500mL of anhydrous tetrahydrofuran, dropwise adding n-butyllithium (62mL,0.15mol) at 10 ℃, heating at 66 ℃ for 1 hour, adding 4, 8-diketone-benzodithiophene (15.5g,0.07mol) at 10 ℃, stirring at room temperature for 3 hours, dropwise adding a solution of tin dichloride (79.5g,0.35mol) dissolved in 250mL of 10% hydrochloric acid at 10 ℃ into the reaction flask, stirring at room temperature for 1 hour, adding 1L of n-hexane, washing the solution 4 times with 200mL of water, drying over anhydrous magnesium sulfate, concentrating to remove the solvent, purifying by chromatography over a silica gel column (column chromatography) to obtain 39.6g of 4, 8-bis (5- (2-hexyldecyl) thiophene-based [1 ] pale yellow liquid, 2-b:4, 5-b' ] dithiophene (compound 31) in 70% yield.
Example 6, preparation of electron donating monomer D2: dithiophene bistrimethyltin.
Bithiophene (compound 32) (10.0g,0.06mol) was charged in a 500mL reaction flask under nitrogen, 300mL of anhydrous tetrahydrofuran was added, 55.3mL of n-butyllithium (0.13 mol) was added dropwise at-60 ℃, stirred at-50 to-60 ℃ for 1 hour, trimethyltin chloride (27.4g,0.13mol) was added at-60 ℃, slowly warmed to room temperature, stirred for 1 hour, 20.0mL of n-hexane was added, washed with 10.0mL of water, dried over anhydrous magnesium sulfate, and concentrated to remove the solvent, to give 14.8g of bisthiophene bistrimethyltin (electron donating monomer D2) as a pale yellow solid in a yield of 50.1%.
The following examples illustrate the preparation of the foregoing random conjugated copolymers.
Example 7: preparation of random conjugated copolymer P1.
Electron donating monomer D1(1.0g,0.88mmol), electron accepting monomer combination M1(0.58g,0.88mmol), tris (2-furyl) phosphine (0.043g,0.14mmol) were placed in a 100mL reaction flask, 70mL of chlorobenzene was added, deoxygenated with argon for 30 minutes, and Pd was added2(dba)3(0.032g,0.03 mol). The reaction was then heated to 130 ℃ for 16 hours. The reaction was cooled to room temperature and the contents of the reaction flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration and the solid was subjected to soxhlet extraction (soxhlet) sequentially with methanol, acetone and dichloromethane. Finally, the residual polymer was taken out and dissolved in chlorobenzene, which was poured into methanol to reprecipitate, and the precipitate was collected by filtration and dried under vacuum to give a dark purple random conjugated copolymer P1(1.1 g). Wherein a, b and c in the random conjugated copolymer P1 represent real numbers in mole fraction, a is 0.25, b is 0.23, c is 0.52, and the sum of a, b and c is 1.
Example 8: preparation of random conjugated copolymer P2.
Electron donating monomer D1(1.0 g)0.88mmol), electron acceptor monomer combination M2(0.58g,0.88mmol), tris (2-furyl) phosphine (0.043g,0.14mmol), placed in a 100mL reaction flask, 70mL of chlorobenzene was added, deoxygenated with argon for 30 minutes, and Pd was added2(dba)3(0.032g,0.03 mol). The reaction was then heated to 130 ℃ for 16 hours. The reaction was cooled to room temperature and the contents of the reaction flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration and the solid was subjected to soxhlet extraction (soxhlet) sequentially with methanol, acetone and dichloromethane. Finally, the residual polymer was taken out and dissolved in chlorobenzene, which was poured into methanol to reprecipitate, and the precipitate was collected by filtration and dried under vacuum to give a dark purple random conjugated copolymer P2(1.1 g). In the random conjugated copolymer P2, a, b, and c represent real numbers in terms of mole fraction, a is 0.07, b is 0.46, c is 0.47, and the sum of a, b, and c is 1.
Example 9: preparation of random conjugated copolymer P3.
Electron donating monomer D1(1.0g,0.88mmol), electron accepting monomer combination M3(0.58g,0.88mmol), tris (2-furyl) phosphine (0.043g,0.14mmol) were placed in a 100mL reaction flask, chlorobenzene 70mL was added, deoxygenated with argon, and Pd was added2(dba)3(0.032g,0.03 mol). The reaction was then heated to 130 ℃ for 16 hours. The reaction was cooled to room temperature and the contents of the reaction flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration and the solid was subjected to soxhlet extraction (soxhlet) sequentially with methanol, acetone and dichloromethane. Finally, the residual polymer was taken out and dissolved in chlorobenzene, which was poured into methanol to reprecipitate, and the precipitate was collected by filtration and dried under vacuum to give a dark purple random conjugated copolymer P3(1.1 g). In the random conjugated copolymer P3, a, b, and c represent real numbers in terms of mole fraction, a is 0.03, b is 0.17, c is 0.80, and the sum of a, b, and c is 1.
Example 10: preparation of random conjugated copolymer P4.
Electron donating monomer D2(1.0g,2.03mmol), electron accepting monomer combination M4(0.25g,2.03mmol), tris (2-furyl) phosphine (0.098g,0.32mmol) were placed in a 100mL reaction flask, chlorobenzene 70mL was added, deoxygenated with argon, and Pd was added2(dba)3(0.073g,0.07 mol). The reaction was then heated to 130 ℃ for 16 hours. The reaction was cooled to room temperature and the contents of the reaction flask were poured into methanol to precipitate a solid. The precipitate was collected by filtration and the solid was subjected to soxhlet extraction (soxhlet) sequentially with methanol, acetone and dichloromethane. Finally, the residual polymer was taken out and dissolved in chlorobenzene, which was poured into methanol to reprecipitate, and the precipitate was collected by filtration and dried under vacuum to give a dark purple random conjugated copolymer P4(1.1 g). Wherein a, b and c in the random conjugated copolymer P4 represent real numbers in mole fraction, a is 0.32, b is 0.19, c is 0.49, and the sum of a, b and c is 1.
Production of organic optoelectronic components
The organic optoelectronic devices of the present invention include, but are not limited to, organic light emitting diodes (oled), organic thin film transistors (tft), organic photovoltaic devices (OPV), and Organic Photodetectors (OPD), and the present invention is exemplified by the organic photovoltaic devices (OPV). Fig. 1 is a sectional view showing a structural example of an organic photovoltaic device used in the present invention, the organic photovoltaic device including: a positive electrode 80, an organic semiconductor layer 90 laminated on the positive electrode 80, and a negative electrode 100 laminated on the organic semiconductor layer 90. In addition, the organic photovoltaic device may further include a substrate 70, and the positive electrode 80 is stacked on the substrate 70.
Fig. 2 is a cross-sectional view showing a structural example in the case where an organic semiconductor layer is laminated, the organic semiconductor layer 90 further includes an electron transport layer 91 laminated over the positive electrode 80, an active layer 92 laminated over the electron transport layer 91, and a hole transport layer 93 laminated over the active layer 92; therefore, the negative electrode 100 is laminated on the hole transport layer 93.
The substrate 70 is preferably a glass substrate or a transparent resin film having mechanical strength and thermal strength and having transparency. Examples of the transparent resin film include: polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, polyether sulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide, and the like.
The positive electrode 80 is preferably formed of a transparent metal Oxide such as Indium or Tin, a composite metal Oxide (Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), or the like), in addition to a metal such as gold, platinum, chromium, or nickel.
The negative electrode 100 may use an alkali metal or an alkaline earth metal, specifically, lithium, magnesium, or calcium. Tin, silver, and aluminum are also preferably used.
In the case of the above-described multilayer structure, it is preferable that at least one of the organic semiconductor layer 90, the electron transport layer 91, the active layer 92, and the hole transport layer 93 contains the random conjugated copolymer.
Production of organic photovoltaic element (OPV): the organic solar cells of examples 11 to 16 and comparative example 1 were prepared in the following manner, and the results are shown in table 1 described later.
Before the preparation of the organic photovoltaic device, the patterned ITO glass substrate (12 Ω/□) was sequentially washed with a detergent, deionized water, acetone and isopropanol in an ultrasonic oscillation tank for 10 minutes. And carrying out surface treatment on the ITO glass substrate for 10 minutes in a UV-ozone cleaning machine after ultrasonic oscillation cleaning. Wherein the glass substrate is the substrate 70, and the ITO is the anode 80.
A branched Polyethyleneimine (PEI) solution was spin-coated on the ITO glass substrate, and baked in air at 100 ℃ for 5 minutes to form a PEI layer, which is the electron transport layer 91. Next, the following comparative example 1 and examples 11 to 14 in Table 1 were usedPolymer and PC61BM was mixed at a weight ratio of 1:1.5 and an active layer solution was prepared using o-xylene as a solvent, and then the active layer solution was spin-coated on the PEI layer, followed by baking at 100 ℃ for 5 minutes in nitrogen to form the active layer 92 on the PEI layer (the electron transport layer 91). Next, Clevios HTL Solar solution (heireis) was spin-coated on the active layer 92, and baked at 120 ℃ for 5 minutes in air to form the aforementioned hole transport layer 93. Then, the anode 100 was heated to deposit Ag metal (about 50nm) as the aforementioned electrode.
The measurement region of the organic photovoltaic device is defined as 0.04cm by the metal shield2. Keithley 2400 as power supply, programmed with Lab-View at 100mW/cm illumination2The electrical properties of the device were measured under simulated sunlight (SAN-EI XES-40S3) at AM1.5G, and the current-voltage curves obtained by recording the electrical properties in a computer program are shown in FIG. 3.
TABLE 1 characteristics of organic photovoltaic elements
| Item | Polymer and method of making same | Voc(V) | Jsc(mA/cm2) | FF(％) | PCE(％) |
| Comparative example 1 | P3HT | 0.573 | 8.24 | 64 | 3.0 |
| Example 11 | Random conjugated copolymer P1 | 0.718 | 13.03 | 64 | 6.0 |
| Example 12 | Random conjugated copolymer P2 | 0.718 | 12.79 | 68 | 6.3 |
| Example 13 | Random conjugated copolymer P3 | 0.720 | 12.89 | 68 | 6.3 |
| Example 14 | Random conjugated copolymer P4 | 0.703 | 13.52 | 64 | 6.0 |
In table 1, Voc denotes an open circuit voltage (open voltage), Jsc denotes a short-circuit current (short-circuit), FF denotes a fill factor (fill factor), and PCE denotes an energy conversion efficiency (energyconversion efficiency). The open circuit voltage and the short circuit current are each the intercepts of the voltage-current density curves in the X-axis and the Y-axis, and when these two values are increased, the efficiency of the organic photovoltaic device is preferably improved. Further, the fill factor is a value that divides the area that can be plotted within the curve by the product of the short circuit current and the open circuit voltage. When the three values of the open-circuit voltage, the short-circuit current, and the fill factor are divided by the light to be irradiated, the energy conversion efficiency can be obtained, and a higher value is preferable. As is apparent from table 1, the energy conversion efficiency of comparative example 1 is 3.0, the energy conversion efficiency of examples 11 and 14 is 2 times that of comparative example 1, and the energy conversion efficiency of examples 12 and 13 is 6.3 times that of comparative example 1, so that the organic photovoltaic element prepared using the random conjugated copolymer of the present invention has high energy conversion efficiency. The open circuit voltage of the comparative example is 0.573, and the open circuit voltage of examples 11 to 14 is 0.703 to 0.720 which is 1.23 to 1.26 times that of comparative example 1, so that the organic photovoltaic device prepared by using the random conjugated copolymer of the present invention has a high open circuit voltage, that is, the organic photovoltaic device has high efficiency. The short-circuit current value of the comparative example is 8.24, and the open-circuit voltage value of examples 11 to 14 is 12.79 to 13.52 times as high as that of comparative example 1, so that the organic photovoltaic device prepared by using the random conjugated copolymer of the present invention has high short-circuit current, i.e., the organic photovoltaic device has high efficiency.
Specifically, the organic photovoltaic device used in the present invention may have a structure as shown in fig. 4, and the organic photovoltaic device includes: the negative electrode 100, the organic semiconductor layer 90 laminated on the negative electrode 100, and the positive electrode 80 laminated on the organic semiconductor layer 90. In addition, the organic photovoltaic device may further include the substrate 70, and the cathode 100 is disposed above the substrate 70. The organic semiconductor layer 90 further includes the hole transport layer 93 laminated on the cathode 100, the active layer 92 laminated on the hole transport layer 93, and the electron transport layer 91 laminated on the active layer 92; therefore, the positive electrode 80 is laminated on the electron transport layer 91. At least one of the organic semiconductor layer 90, the electron transport layer 91, the active layer 92, and the hole transport layer 93 comprises the random conjugated copolymer described above.
While the invention has been disclosed and illustrated with respect to certain specific embodiments thereof, it should be apparent to those skilled in the art that the invention is susceptible to various other embodiments. Therefore, the protection scope of the present invention is subject to the scope defined by the appended claims.
Claims (10)
1. A random conjugated copolymer, wherein it is represented by formula I:
a. b and c represent real numbers of mole fractions, a is more than or equal to 0.005 and less than or equal to 0.99, b is more than or equal to 0.005 and less than or equal to 0.99, c is more than or equal to 0.005 and less than or equal to 0.99, and the sum of a, b and c is 1;
a is at least one group selected from the group consisting of:
z is O, S, Se, NR2Or
n0Is 0, 1 or 2;
R1is H, F, Cl, -CN group, R16、-OR17radical-SR18Radical, -C (═ O) OR19A group, aryl or heteroaryl; and, R2To R19Each independently is a linear, branched or cyclic alkyl group having from 4 to 30 carbons, or each independently is an alkenyl or alkynyl group having from 4 to 30 carbons in the chain, or each independently is an alkyl, alkenyl or alkynyl group having from 4 to 30 carbons in the chain in which one or more H's are substituted with a halogen, -CN group or-Si group;
Ar1and Ar2Each independently is:
n1and n2Is 1,2 or 3;
R20to R23Each independently is a linear, branched or cyclic alkyl group having from 4 to 30 carbons, or each independently is an alkenyl or alkynyl group having from 4 to 30 carbons in the chain, or each independently is an alkyl, alkenyl or alkynyl group having from 4 to 30 carbons in the chain in which one or more H's are substituted with a halogen, -CN group or-Si group; or R20To R23Each independently is H, F, Cl, -CN group, -OR24radical-SR25Radical, -C (═ O) OR26A group, aryl or heteroaryl; and, R24To R26Each independently is a linear, branched or cyclic alkyl group having from 4 to 30 carbons, or each independently is an alkenyl or alkynyl group having from 4 to 30 carbons in the chain, or each independently is an alkyl, alkenyl or alkynyl group having from 4 to 30 carbons in the chain in which one or more H's are substituted with a halogen, -CN group or-Si group;
d is
R27To R28Each independently is H, F, Cl, R29-CN group, -OR30radical-SR31Radical, -C (═ O) OR32Radical, aryl, heteroaryl or-Si (R)33)3A group;
R29to R33Each independently is a linear, branched or cyclic alkyl group having from 4 to 30 carbons, or each independently is an alkenyl or alkynyl group having from 4 to 30 carbons in the chain, or each independently is an alkyl, alkenyl or alkynyl group having from 4 to 30 carbons in the chain in which one or more H's are substituted with a halogen, -CN group or-Si group;
aryl is
Heteroaryl is
n3And n4Is 1,2, 3, 4 or 5;
R34to R37Each independently is H, F, Cl, R38-CN group, -OR39radical-SR40Radical, -C (═ O) OR41Radical or-Si (R)42)3A group;
R38to R42Each independently is a linear, branched or cyclic alkyl group having from 4 to 30 carbons, or each independently is an alkenyl or alkynyl group having from 4 to 30 carbons in the chain, or each independently is an alkyl, alkenyl or alkynyl group having from 4 to 30 carbons in the chain in which one or more H's are substituted with a halogen, -CN group or-Si group;
R43to R48Each independently is H, F, Cl, R49-CN group, -OR50radical-SR51Radical, -C (═ O) OR52Radical or-Si (R)53)3A group; and the number of the first and second groups,
R49to R53Each independently is a linear, branched or cyclic alkyl group having from 4 to 30 carbons, or each independently is an alkenyl or alkynyl group having from 4 to 30 carbons in the chain, or each independently is an alkyl, alkenyl or alkynyl group having from 4 to 30 carbons in the chain in which one or more H groups are substituted with a halogen, -CN group or-Si group.
2. The random conjugated copolymer of claim 1, wherein the random conjugated copolymer is comprised of three repeating units in a random arrangement; the three repeating units are respectively a first repeating unit structure, a second repeating unit structure and a third repeating unit structure, and the- [ D-Ar ] in the formula I1-A-Ar1]-is a first repeating unit structure, - [ D-Ar ] in said formula I2-A-Ar2]-is a second repeating unit structure, in said formula I- [ D-Ar1-A-Ar2]-is a third repeating unit structure.
3. A method for producing a random conjugated copolymer, which is used for producing the random conjugated copolymer according to claim 1, characterized by comprising at least the steps of:
adding Br-A-Br and Ar1-SnBu3And Ar2-SnBu3Mixing with palladium catalyst to perform coupling reaction and obtain mixture containing Ar1-A-Ar2、Ar1-A-Ar1And Ar2-A-Ar2；
Subjecting the resulting mixture to bromination to obtain the following electron acceptor monomer combination of three electron acceptor monomers: Br-Ar1-A-Ar2-Br、Br-Ar1-A-Ar1Br and Br-Ar2-A-Ar2-Br；
Combining the electron acceptor monomer thus obtained with an electron donating monomer Me3Sn-D-SnMe3Carrying out a polymerization reaction to obtain the random conjugated copolymer;
wherein Me is methyl, Bu is butyl, Br is bromine, Sn is tin A, D, Ar1And Ar2A, D, Ar according to claim 11And Ar2Have the same meaning.
4. A method for producing a random conjugated copolymer, which is used for producing the random conjugated copolymer according to claim 1, characterized by comprising at least the steps of:
adding Br-A-Br and Ar1-SnBu3Mixing with palladium catalyst for coupling reaction;
adding Ar after the reaction reaches the expected condition2-SnBu3Continuing the reaction and obtaining a mixture comprising Ar1-A-Ar2、Ar1-A-Ar1And Ar2-A-Ar2；
Subjecting the resulting mixture to bromination to obtain the following electron acceptor monomer combination of three electron acceptor monomers: Br-Ar1-A-Ar2-Br、Br-Ar1-A-Ar1Br and Br-Ar2-A-Ar2-Br；
The obtained electronsAcceptor monomer combination and electron donating monomer Me3Sn-D-SnMe3Carrying out a polymerization reaction to obtain the random conjugated copolymer;
wherein Me is methyl, Bu is butyl, Br is bromine, Sn is tin A, D, Ar1And Ar2A, D, Ar according to claim 11And Ar2Have the same meaning.
5. An organic photovoltaic element comprising the random conjugated copolymer according to claim 1.
6. The organic photovoltaic element according to claim 5, wherein the organic photovoltaic element comprises at least: a positive electrode (80), an organic semiconductor layer (90) laminated on the positive electrode (80), and a negative electrode (100) laminated on the organic semiconductor layer (90), wherein the organic semiconductor layer (90) contains the random conjugated copolymer.
7. The organic photovoltaic device according to claim 6, further comprising a substrate (70), wherein the positive electrode (80) is laminated on the substrate (70) or the negative electrode (100) is disposed under the substrate (70).
8. The organic photovoltaic device according to claim 7, wherein the organic semiconductor layer (90) further comprises an electron transport layer (91) laminated over the positive electrode (80), an active layer (92) laminated over the electron transport layer (91), and a hole transport layer (93) laminated over the active layer (92); the negative electrode (100) is laminated above the hole transport layer (93); at least one of the electron transport layer (91), the active layer (92), and the hole transport layer (93) includes the random conjugated copolymer.
9. The organic photovoltaic element according to claim 5, wherein the organic photovoltaic element comprises at least: the organic light-emitting diode comprises a substrate (70), a negative electrode (100) arranged above the substrate (70), an organic semiconductor layer (90) laminated above the negative electrode (100), and a positive electrode (80) laminated above the organic semiconductor layer (90), wherein the organic semiconductor layer (90) comprises the random conjugated copolymer.
10. The organic photovoltaic device according to claim 9, wherein the organic semiconductor layer (90) further comprises a hole transport layer (93) laminated over the negative electrode (100), an active layer (92) laminated over the hole transport layer (93), and an electron transport layer (91) laminated over the active layer (92); the positive electrode (80) is laminated above the electron transport layer (91); at least one of the electron transport layer (91), the active layer (92), and the hole transport layer (93) includes the random conjugated copolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW107130189A TWI677513B (en) | 2018-08-29 | 2018-08-29 | Random conjugated copolymer, its preparation method and its application on organic optoelectronic elements |
| TW107130189 | 2018-08-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110872378A true CN110872378A (en) | 2020-03-10 |
Family
ID=69189182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811142925.4A Pending CN110872378A (en) | 2018-08-29 | 2018-09-28 | Random conjugated copolymer, preparation method thereof and application thereof in organic photoelectric element |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN110872378A (en) |
| TW (1) | TWI677513B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061235A (en) * | 2021-03-22 | 2021-07-02 | 位速科技股份有限公司 | Copolymer and organic photovoltaic element |
| CN114573794A (en) * | 2020-11-30 | 2022-06-03 | 位速科技股份有限公司 | Conjugated polymer and organic photovoltaic element |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI723753B (en) * | 2020-01-21 | 2021-04-01 | 位速科技股份有限公司 | Copolymer and organic photovoltaic element |
| TWI753676B (en) * | 2020-11-26 | 2022-01-21 | 位速科技股份有限公司 | Conjugated polymers and organic photovoltaic elements |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103229322A (en) * | 2010-10-22 | 2013-07-31 | 破立纪元有限公司 | Conjugated polymers and their use in optoelectronic devices |
| CN107057044A (en) * | 2017-03-03 | 2017-08-18 | 南方科技大学 | A kind of diazosulfide base polymer donor material of exotic atom substitution and its preparation method and application |
| WO2018017344A1 (en) * | 2016-07-19 | 2018-01-25 | Phillips 66 Company | Unsymmetrical benzothiadiazole-based molecular complexes |
| EP3333170A1 (en) * | 2016-12-06 | 2018-06-13 | Merck Patent GmbH | Asymmetrical polycyclic compounds for use in organic semiconductors |
| CN108431076A (en) * | 2016-01-09 | 2018-08-21 | 飞利斯有限公司 | Dithiophene thiadiazoles semiconductor and related device |
-
2018
- 2018-08-29 TW TW107130189A patent/TWI677513B/en active
- 2018-09-28 CN CN201811142925.4A patent/CN110872378A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103229322A (en) * | 2010-10-22 | 2013-07-31 | 破立纪元有限公司 | Conjugated polymers and their use in optoelectronic devices |
| CN108431076A (en) * | 2016-01-09 | 2018-08-21 | 飞利斯有限公司 | Dithiophene thiadiazoles semiconductor and related device |
| WO2018017344A1 (en) * | 2016-07-19 | 2018-01-25 | Phillips 66 Company | Unsymmetrical benzothiadiazole-based molecular complexes |
| EP3333170A1 (en) * | 2016-12-06 | 2018-06-13 | Merck Patent GmbH | Asymmetrical polycyclic compounds for use in organic semiconductors |
| CN107057044A (en) * | 2017-03-03 | 2017-08-18 | 南方科技大学 | A kind of diazosulfide base polymer donor material of exotic atom substitution and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| DAIZE MO ETAL.: "Chlorination of Low-Band-Gap Polymers: Toward High-Performance Polymer Solar Cells", 《CHEMISTRY OF MATERIALS》 * |
| HUI CHEN ETAL.: "A Chlorinated p-Conjugated Polymer Donor for Efficient Organic Solar Cells", 《JOULE》 * |
| 吴其胜: "《新能源材料 第2版》", 31 July 2017, 上海：华东理工大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573794A (en) * | 2020-11-30 | 2022-06-03 | 位速科技股份有限公司 | Conjugated polymer and organic photovoltaic element |
| CN114573794B (en) * | 2020-11-30 | 2023-09-15 | 位速科技股份有限公司 | Conjugated polymer and organic photovoltaic element |
| CN113061235A (en) * | 2021-03-22 | 2021-07-02 | 位速科技股份有限公司 | Copolymer and organic photovoltaic element |
| CN113061235B (en) * | 2021-03-22 | 2023-08-08 | 位速科技股份有限公司 | Copolymer and organic photovoltaic element |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI677513B (en) | 2019-11-21 |
| TW202009249A (en) | 2020-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101946076B1 (en) | Photovoltaic cell containing novel photoactive polymer | |
| EP2321861B1 (en) | Novel photoactive co- polymers | |
| CN110872378A (en) | Random conjugated copolymer, preparation method thereof and application thereof in organic photoelectric element | |
| JP5746226B2 (en) | Cyclopentadienedithiophene-quinoxaline copolymer, production method thereof, and application thereof | |
| JP5501526B2 (en) | Quinoxaline conjugated polymer containing fused-ring thiophene units, method for producing the conjugated polymer and application thereof | |
| JP5425338B2 (en) | Copolymer containing anthracene and pearselenol, its production method and its application | |
| CN110291129B (en) | Polymer and organic solar cell comprising same | |
| CN103360604A (en) | Conjugated metal polymer photoelectric material with functionalized polarity side-chain radicals and application thereof | |
| KR20120000522A (en) | Electron donating polymer and organic solar cell including the same | |
| JP5612757B2 (en) | Fluorene copolymers, process for producing the same and use thereof | |
| JP5688420B2 (en) | Fluorenyl-containing porphyrin-benzene copolymer and method for producing the same | |
| KR20210073470A (en) | Novel polymer and organic electronic device using them | |
| CN112708112A (en) | Conjugated polymer and organic photovoltaic element | |
| JP5667693B2 (en) | Quinoxaline unit-containing porphyrin copolymer, method for producing the same, and application thereof | |
| CN110734540A (en) | conjugated polymer containing halogen atom substituted thienyl fused thiazole structure and application thereof | |
| KR102114177B1 (en) | Novel compound, its production method and organic electronic device using them | |
| KR20130083125A (en) | Organic photovoltain polymer and manufacturing method thereof | |
| Tong et al. | Synthesis of π-extended dithienobenzodithiophene-containing medium bandgap copolymers and their photovoltaic application | |
| KR101666353B1 (en) | Mid Band-gap conjugated polymers and method for manufacturing thereof and organo-electronic devices using the same | |
| KR101777326B1 (en) | Electron donating polymer and organic solar cell including the same | |
| KR102130593B1 (en) | Composition for forming self-healing photoactive layer and Organic solar cells comprising the same | |
| KR20130038548A (en) | The organic photovoltaic polymer containing phenazine derivative and manufacturing method thereof | |
| CN108570141B (en) | Conjugated polymer containing alkylcarbonylbithiophene, and preparation method and application thereof | |
| JP5443655B2 (en) | Porphyrin copolymer containing thienothiadiazole unit, method for producing the copolymer and application thereof | |
| TWI826020B (en) | Copolymers, active layers and organic photovoltaic components |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |